Ruthenocene derivatives

Ferrocen- und Ruthenocen-Derivate 2,2-Dimethylpropan-dioladipat Oder Carbowax 20 M 535,536)... 

Similar to ferrocene, the ruthenocene derivatives (89) substituted with a CR R group are greatly stabilized in comparison to noncomplexed carbenes or carbonium ions. In fact, from the enhanced barrier to internal rotation in the a-ruthenocenyl carbonium ion Ru-CHMe+ (>130kJmol ) compared with the related ferrocene derivative (70kJmol ), even greater stabilization in ruthenocene is expected. 

Ruthenocene derivatives have also been studied as potential second-order nonlinear optical materials. Using the [Cp Ru]+ fragment, several aromatic systems have been synthesized and studied for this goal. The [Cp Ru]+ fragment was synthesized by treating [Cp Ru(OMe)]2 with triflic acid. Various aromatic... 

Ruthenocene and osmocene are obtained in good yields from TlCp and [M(COD)Cl2], Several mixed-ligand ruthenocene derivatives are prepared from [Ru(Cp -r )Cl2]2 (Table 7). The latter is derived from the reaction of RuCl3-nH20 and Cp H in refluxing ethanoP ". Similar conditions with added PMCj give Ru(Cp - )Cl(PMe3)2. 

Aromatization of the ligand is a major driving force in the C-C bond-cleavage reaction. For example, sp C-sp C bond cleavage in (pentamethylcydohexadienyl)ruthe-nium is reported to give ruthenocene derivatives (Scheme 14.23) [54]. In this reaction, a Bronsted base is believed to promote demethylation from the exo face similar reactions are documented for cationic ruthenium(II) complexes [55-57]. 

The Cp Ru(ii) fragment, easily available as the tris(acetonitrile) complex salt [Cp Ru(NCMe)3]CF3S03, has been reported as a very well suited building block for the formation of cationic mixed Cp -arene donor systems [73], This constitutes an alternative to ruthenocene derivatives that do not afford the corresponding ruthenocenium salts on oxidation, but usually readily decompose [74]. Since the Cp Ru(ii) fragment has a high affinity for arenes, a number of mono-, di-, and... 

The research on ferrocene-containing thermotropic liquid crystals has concentrated, so far, on design, synthesis, and investigations of thermal properties. These efforts, and more particularly the results obtained, could be a source of inspiration for the development of new metallomesogens. As an example, we recently reported the first liquid crystalline ruthenocene derivatives [29]. 

Alain, V., Blanchard-Desce, M., Chen, C.-T., Marder, S.R., Fort, A., Barzoukas, M. Large optical nonlinearities with conjugated ferrocene and ruthenocene derivatives. Synth. Met. 81, 133—136... 

Poulsen and coworkers have studied the effect of ferrocene and ruthenocene as substituents on benzenesulfonamides (Figure 1.13) [103]. Metallocene derivatives 26-29 showed good binding affinity toward CAs. Ruthenocene derivative 27 was the most active compound against the relevant carbonic anhydrase hCA... 

Figure 1.12 Cocrystal structure of sulfonamide ruthenocene derivative 27 bound to carbonic anhydrase hCAii (PDB code 3P44) [102). Oniy amino acid residues close enough for interactions with the ligand and Zn " are...

Some chemistry of ruthenocene derivatives is given below. 

Acetyl osmocene was reduced to hydroxyethylosmocene in 97% yield by the procedure given for the ruthenocene derivative and sublimed from alumina at 175 and 1mm to give a 55% yield of vinyl osmocene, mp. 59 . The IR and NMR spectra of the hydroxyethyl osmocene and vinylosmocene resemble closely the corresponding ferrocene and ruthenocene derivatives and agree with previously published results. ... 

Enders et aL reported the first example of adduct formation between Zn and ruthenocene derivatives, complex... 

SCHEME 4.181 Microwave-assisted phosphination of a ruthenocene derivative [271]. 

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